U.S. patent application number 13/133176 was filed with the patent office on 2012-05-03 for long-wear, waterproof and washable mascara composition.
This patent application is currently assigned to L'OREAL S.A.. Invention is credited to Bruno Bavouzet, Hy Si Bui, Mohamed Kanji, Chunhua Li, Anita Chon Tong.
Application Number | 20120107263 13/133176 |
Document ID | / |
Family ID | 42310124 |
Filed Date | 2012-05-03 |
United States Patent
Application |
20120107263 |
Kind Code |
A1 |
Bui; Hy Si ; et al. |
May 3, 2012 |
LONG-WEAR, WATERPROOF AND WASHABLE MASCARA COMPOSITION
Abstract
The present invention is directed to long wear, washable and
waterproof eye makeup composition containing: (a) at least one
polyamine; (b) at least one oil-soluble polar modified polymer; (c)
water; (d) at least one non-volatile oil capable of solublizing the
oil-soluble polar modified polymer; (d) at least one volatile
solvent; (e) optionally, at least one colorant; and (f) optionally,
at least one wax, wherein the composition does not require a latex
film former or surfactant/emulsifier.
Inventors: |
Bui; Hy Si; (Piscataway,
NJ) ; Kanji; Mohamed; (Edison, NJ) ; Tong;
Anita Chon; (Garwood, NJ) ; Bavouzet; Bruno;
(Hoboken, NJ) ; Li; Chunhua; (Scotch Plains,
NJ) |
Assignee: |
L'OREAL S.A.
Paris
FR
|
Family ID: |
42310124 |
Appl. No.: |
13/133176 |
Filed: |
December 9, 2009 |
PCT Filed: |
December 9, 2009 |
PCT NO: |
PCT/US09/67332 |
371 Date: |
August 2, 2011 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61120890 |
Dec 9, 2008 |
|
|
|
Current U.S.
Class: |
424/70.7 ;
132/200 |
Current CPC
Class: |
A61Q 1/10 20130101; A61K
8/84 20130101; A61K 8/92 20130101; A61K 8/064 20130101; A61K 8/06
20130101 |
Class at
Publication: |
424/70.7 ;
132/200 |
International
Class: |
A61K 8/92 20060101
A61K008/92; A61Q 1/10 20060101 A61Q001/10 |
Claims
1. A water-in-oil mascara composition comprising: (a) at least one
polyamine; (b) at least one oil-soluble polar modified polymer; (c)
water; (d) at least one non-volatile oil capable of solubilizing
the oil-soluble polar modified polymer; and (e) at least one
volatile solvent.
2. The composition of claim 1 wherein the polyamine is a branched
polyethyleneimine.
3. The composition of claim 1, wherein the composition is made
using from 0.05 to 20% by weight, based on the weight of the
composition, of the polyamine.
4. The composition of claim 1, wherein the composition is made
using from 1 to 30% by weight, based on the weight of the
composition, of the polar modified polymer.
5. The composition of claim 1 wherein water is present in an amount
of from 5% to 50% by weight, based on the weight of the
composition.
6. The composition of claim 1 wherein the non-volatile oil is
present in an amount of from 0.5% to 15% by weight, based on the
weight of the composition.
7. The composition of claim 1 wherein the volatile solvent is
present in an amount of from 5% to 80% by weight, based on the
weight of the composition.
8. The composition of claim 1 wherein the composition has a
critical yield strain of from about 1% to about 500%.
9. The composition of claim 1 wherein the composition has a shear
thinning slope of from about -0.65 to about -0.99.
10. The composition of claim 1 wherein the composition has a
storage modulus of from about 10 Pa to about 5000 Pa.
11. A method of making-up eyelashes comprising applying onto the
eyelashes a composition according to claim 1.
12. A water-in-oil mascara composition comprising: (a) a reaction
product of at least one polyamine and at least one oil-soluble
polar modified polymer; (b) water; (c) at least one non-volatile
oil capable of solubilizing the oil-soluble polar modified polymer;
(d) at least one volatile solvent; and (e) optionally, at least one
colorant.
13. The composition of claim 12, wherein the polyamine is a
branched polyethyleneimine.
14. The composition of claim 1, wherein the composition is made
using from 0.05 to 20% by weight, based on the weight of the
composition, of the polyamine.
15. The composition of claim 1, wherein the composition is made
using from 1 to 30% by weight, based on the weight of the
composition, of the polar modified polymer.
16. The composition of claim 1, wherein water is present in an
amount of from 5% to 50% by weight, based on the weight of the
composition.
17. The composition of claim 1, wherein the non-volatile oil is
present in an amount of from 0.5% to 15% by weight, based on the
weight of the composition.
18. A method of making-up eyelashes comprising applying onto the
eyelashes a composition according to claim 12.
19. A method of removing the mascara composition of claim 1 from
eyelashes comprising applying water to the mascara composition in
an amount sufficient to remove the composition from the eyelashes.
Description
FIELD OF THE INVENTION
[0001] The present invention generally relates to a novel mascara
composition and method of making-up eyes. More particularly, the
present invention relates to a mascara composition which is
long-wear, waterproof and washable.
DISCUSSION OF THE BACKGROUND
[0002] It is well known in the industry that one way of making a
mascara composition which is both waterproof and long wear is to
make it anhydrous. Thus, the composition will typically comprise
volatile solvents and film forming polymers. This type of
composition, however, is not washable with water.
[0003] Conventional mascara compositions which are both washable
and long wear, but not waterproof, require the use of latex film
formers in combination with an oil-in-water emulsion.
[0004] The use of latex film formers to form such mascara
compositions has numerous drawbacks. First, latex film formers are
somewhat expensive and require large amounts thereof to be used,
consequently, adding to the cost of the finished goods. Secondly,
latex film formers can be difficult to formulate with due to the
large solid content load required, thus making them unstable, as
is, or sensitive to added ingredients.
[0005] Therefore, it is an object of the present invention to
provide an eye makeup composition which is waterproof, long wear
and washable which, preferably, has a unique gel-like texture and
feel, without the need for having to use latex film formers or
surfactants/emulsifiers.
SUMMARY OF THE INVENTION
[0006] The present invention relates to a mascara composition
containing:
(a) at least one polyamine; (b) at least one oil-soluble polar
modified polymer; (c) water; (d) at least one non-volatile oil
capable of solubilizing the oil-soluble polar modified polymer; (e)
at least one volatile solvent; and (f) optionally, at least one
colorant.
[0007] The present invention also relates to a mascara composition
containing:
(a) a reaction product of at least one polyamine and at least one
oil-soluble polar modified polymer; (b) water; (c) at least one
non-volatile oil capable of solubilizing the oil-soluble polar
modified polymer; (d) at least one volatile solvent; and (e)
optionally, at least one colorant.
[0008] The present invention relates to a mascara composition made
by combining:
(a) at least one polyamine; (b) at least one oil-soluble polar
modified polymer; (c) water; (c) at least one non-volatile oil
capable of solubilizing the oil-soluble polar modified polymer; (d)
at least one volatile solvent; and (e) optionally, at least one
colorant.
[0009] Preferably, the composition does not require a latex film
former or surfactant/emulsifier.
[0010] The present invention also relates to methods of making up
eyelashes involving applying the above-disclosed composition onto
the eyelashes.
[0011] The present invention further relates to removing the
above-disclosed mascara composition from eyelashes by applying
water to the mascara composition in an amount sufficient to remove
the composition from the eyelashes.
DETAILED DESCRIPTION OF THE INVENTION
[0012] "Film former" or "film forming agent" or "film forming
resin" as used herein means a polymer which, after dissolution in
at least one solvent (such as, for example, water and organic
solvents), leaves a film on the substrate to which it is applied,
for example, once the at least one solvent evaporates, absorbs
and/or dissipates on the substrate.
[0013] "Tackiness", as used herein, refers to the adhesion between
two substances. For example, the more tackiness there is between
two substances, the more adhesion there is between the
substances.
[0014] "Keratinous substrates", as used herein, include but are not
limited to, skin, hair and nails.
[0015] "Substituted" as used herein, means comprising at least one
substituent. Non-limiting examples of substituents include atoms,
such as oxygen atoms and nitrogen atoms, as well as functional
groups, such as hydroxyl groups, ether groups, alkoxy groups,
acyloxyalky groups, oxyalkylene groups, polyoxyalkylene groups,
carboxylic acid groups, amine groups, acylamino groups, amide
groups, halogen containing groups, ester groups, thiol groups,
sulphonate groups, thiosulphate groups, siloxane groups, and
polysiloxane groups. The substituent(s) may be further
substituted.
[0016] As defined herein, stability is tested by placing the
composition in a controlled environment chamber for 8 weeks at
25.degree. C. In this test, the physical condition of the sample is
inspected as it is placed in the chamber. The sample is then
inspected again at 24 hours, 3 days, 1 week, 2 weeks, weeks and 8
weeks. At each inspection, the sample is examined for abnormalities
in the composition such as phase separation if the composition is
in the form of an emulsion, bending or leaning if the composition
is in stick form, melting, or syneresis (or sweating). The
stability is further tested by repeating the 8-week test at
37.degree. C., 40.degree. C., 45.degree. C., 50.degree. C., and
under freeze-thaw conditions. A composition is considered to lack
stability if in any of these tests an abnormality that impedes
functioning of the composition is observed. The skilled artisan
will readily recognize an abnormality that impedes functioning of a
composition based on the intended application.
[0017] "Volatile", as used herein, means having a flash point of
less than about 100.degree. C.
[0018] "Non-volatile", as used herein, means having a flash point
of greater than about 100.degree. C.
[0019] As used herein, the expression "at least one" means one or
more and thus includes individual components as well as
mixtures/combinations.
[0020] Other than in the operating examples, or where otherwise
indicated, all numbers expressing quantities of ingredients and/or
reaction conditions are to be understood as being modified in all
instances by the term "about," meaning within 10% to 15% of the
indicated number.
[0021] "Waterproof" as used herein refers to the ability to repel
water and permanence with respect to water. Waterproof properties
may be evaluated by any method known in the art for evaluating such
properties. For example, a mascara composition may be applied to
false eyelashes, which may then be placed in water for a certain
amount of time, such as, for example, 20 minutes. Upon expiration
of the pre-ascertained amount of time, the false eyelashes may be
removed from the water and passed over a material, such as, for
example, a sheet of paper. The extent of residue left on the
material may then be evaluated and compared with other
compositions, such as, for example, commercially available
compositions. Similarly, for example, a composition may be applied
to skin, and the skin may be submerged in water for a certain
amount of time. The amount of composition remaining on the skin
after the pre-ascertained amount of time may then be evaluated and
compared. For example, a composition may be waterproof if a
majority of the product is left on the wearer, e.g., eyelashes,
skin, etc. In a preferred embodiment of the present invention,
little or no composition is transferred from the wearer.
[0022] "Long wear" compositions as used herein, refers to
compositions where color remains the same or substantially the same
as at the time of application, as viewed by the naked eye, after an
extended period of time. Long wear properties may be evaluated by
any method known in the art for evaluating such properties. For
example, long wear may be evaluated by a test involving the
application of a composition to human hair, skin or lips and
evaluating the color of the composition after an extended period of
time. For example, the color of a composition may be evaluated
immediately following application to hair, skin or lips and these
characteristics may then be re-evaluated and compared after a
certain amount of time. Further, these characteristics may be
evaluated with respect to other compositions, such as commercially
available compositions.
Polyamine Compound
[0023] According to the present invention, compositions comprising
at least one polyamine compound are provided. In accordance with
the present invention, the polyamine compound has at least two
primary amine groups available to react with hydrophilic groups of
the oil-soluble polar modified polymer.
[0024] According to particularly preferred embodiments, the
polyamine compound is a polyalkyleneimine, preferably a C2-C5
polyalkyleneamine compound, more preferably a polyethyleneimine or
polypropyleneimine. Most preferably, the polyalkylenamine is
polyethyleneimine ("PEI"). The polyalkyleneamine compound
preferably has an average molecular weight range of from
500-200,000, including all ranges and subranges therebetween.
[0025] According to preferred embodiments, compositions of the
present invention contain polyethyleneimine compounds in the form
of branched polymers. Commercially available examples of such
polymers are available from BASF under the tradename LUPASOL or
POLYIMIN. Non-limiting examples of such polyethyleneimines include
Lupasol.RTM. PS, Lupasol.RTM. PL, Lupasol.RTM. PR8515, Lupasol.RTM.
G20, Lupasol.RTM. G35.
[0026] According to other embodiments of the present invention,
polyamines such as polyethyleneimines and polypropyleneimines can
be in the form of dendrimers. Non-limiting examples of such
dendrimers are manufactured by the company DSM, and/or are
disclosed in U.S. Pat. No. 5,530,092 and U.S. Pat. No. 5,610,268,
the contents of which are hereby incorporated by reference.
Commercially available examples of such polymers include
polyamidoamine or polypropyleneimine polymers from DENDRITECH sold
under the STARBURST.degree. name.
[0027] According to other embodiments of the present invention,
derivatives of polyalkyleneamines are suitable polyamines. Such
derivatives include, but are not limited to, alkylated derivatives,
the addition products of alkylcarboxylic acids to
polyalkyleneamines, the addition products of ketones and of
aldehydes to polyalkyleneamines, the addition products of
isocyanates and of isothiocyanates to polyalkyleneamines, the
addition products of alkylene oxide or of polyalkylene oxide block
polymers to polyalkyleneamines, quaternized derivatives of
polyalkyleneamines, the addition products of a silicone to
polyalkyleneamines, and copolymers of dicarboxylic acid and
polyalkyleneamines. Even further suitable polymamines include, but
are not limited to, polyvinylimidazoles (homopolymers or
copolymers), polyvinylpyridines (homopolymers or copolymers),
compounds comprising vinylimidazole monomers (see, for example,
U.S. Pat. No. 5,677,384, hereby incorporated by reference), and
polymers based on amino acids containing a basic side chain
(preferably selected from proteins and peptides comprising at least
5%, preferably at least 10% of amino acids selected from histidine,
lysine and arginine). Such suitable polyamines as described above
include those disclosed and described in U.S. Pat. No. 6,162,448,
the contents of which are hereby incorporated by reference.
Commercially available examples of such polymers include
polyvinylamine/formamide such as those sold under the Lupamine.RTM.
name by BASF, chitosan from vegetable origin such as those sold
under the Kiosmetine.RTM. or Kitozyme.RTM. names, or copolymer 845
sold by ISP.
[0028] According to preferred embodiments, the at least one
polyamine compound is present in the composition of the present
invention in an amount ranging from about 0.1 to about 10% by
weight, more preferably from about 0.2 to about 5% by weight, based
on the total weight of the composition, including all ranges and
subranges within these ranges.
[0029] Preferably, the amount of polyamine compound reacted with
the oil-soluble polar modified polymer is such that at least two
amine groups on the polyamine compound react with the oil-soluble
polar modified polymer to form links or bonds between the amine
groups and the hydrophilic groups of the oil-soluble polar modified
polymer. The appropriate amount of polyamine compound to react with
the oil-soluble polar modified polymer to obtain a reaction product
can be easily determined, taking into account the number/amount of
reactive amine groups on the polyamine compound and the
number/amount of corresponding reactive groups on the oil-soluble
polar modified polymer (for example, maleic anhydride groups).
According to preferred embodiments, excess oil-soluble polar
modified polymer (as determined by the relative number/amount of
corresponding reactive groups on the polymer as compared to the
reactive amine groups on the polyamine) is reacted with polyamine.
Preferably, the polyamine to oil-soluble polar modified ratio is
between 0.005 and 1, preferably between 0.006 and 0.5, and
preferably between 0.007 and 0.1, including all ranges and
subranges therebetween.
[0030] Oil-Soluble Polar Modified Polymer
[0031] According to the present invention, compositions comprising
at least one oil-soluble polar modified polymer are provided.
"Polar modified polymer" as used herein refers to a hydrophobic
homopolymer or copolymer which has been modified with hydrophilic
unit(s). "Oil-soluble" as used herein means that the polar modified
polymer is soluble in oil.
[0032] Suitable monomers for the hydrophobic homopolymers and/or
copolymers include, but are not limited to, cyclic, linear or
branched, substituted or unsubstituted, C2-C20 compounds such as,
for example, styrene, ethylene, propylene, isopropylene, butylene,
isobutylene, pentene, isopentene, isoprene, hexene, isohexene,
decene, isodecene, and octadecene, including all ranges and
subranges therebetween. Preferably, the monomers are C2-C8
compounds, more preferably C2-C6 compounds, and most preferably
C2-C4 compounds such as ethylene, propylene and butylene.
[0033] Suitable hydrophilic unit(s) include, but are not limited
to, maleic anhydride, acrylates, alkyl acrylates such as, for
example, methyl acrylate, ethyl acrylate, propyl acrylate, and
butyl acrylate, and polyvinylpyrrolidone (PVP).
[0034] According to the present invention, the polar modified
polymer is oil-soluble: that is, the polymer does not contain a
sufficient amount of hydrophilic unit(s) to render the entire
polymer water-soluble or oil-insoluble. According to preferred
embodiments, the polar modified polymer contains the same amount of
hydrophobic monomer as hydrophilic unit (1:1 ratio) or more
hydrophobic monomer than hydrophilic unit. According to
particularly preferred embodiments, the polar modified polymer
contains 50% or less hydrophilic unit(s) (based on weight of the
polymer), 40% or less hydrophilic unit(s), 30% or less hydrophilic
unit(s), 20% or less hydrophilic unit(s), 10% or less hydrophilic
unit(s), 5% or less hydrophilic unit(s), 4% or less hydrophilic
unit(s), or 3% or less hydrophilic unit(s).
[0035] Preferably, the polar modified polymer has from about 0.5%
to about 10% hydrophilic units, more preferably from about 1% to
about 8% hydrophilic units by weight with respect to the weight of
the polymer, including all ranges and subranges therebetween.
Particularly preferred hydrophilically modified polymers are
ethylene and/or propylene homopolymers and copolymers which have
been modified with maleic anhydride units.
[0036] According to preferred embodiments of the present invention,
the polar modified polymer is a wax. According to particularly
preferred embodiments, the polar modified wax is made via
metallocene catalysis, and includes polar groups or units as well
as a hydrophobic backbone. Suitable modified waxes include those
disclosed in U.S. patent application publication no. 20070031361,
the entire contents of which is hereby incorporated by reference.
Particularly preferred polar modified waxes are C2-C3 polar
modified waxes.
[0037] In accordance with preferred embodiments of the present
invention, the polar modified wax is based upon a homopolymer
and/or copolymer wax of hydrophobic monomers and has a
weight-average molecular weight Mw of less than or equal to 25 000
g/mol, preferably of 1000 to 22 000 g/mol and particularly
preferably of 4000 to 20,000 g/mol, a number-average molecular
weight Mn of less than or equal to 15 000 g/mol, preferably of 500
to 12 000 g/mol and particularly preferably of 1000 to 5000 g/mol,
a molar mass distribution Mw/Mn in the range from 1.5 to 10,
preferably from 1.5 to 5, particularly preferably from 1.5 to 3 and
especially preferably from 2 to 2.5, which have been obtained by
metallocene catalysis. Also, the polar modified wax preferably has
a melting point above 75.degree. C., more preferably above
90.degree. C. such as, for example, a melting point between
90.degree. C. and 160.degree. C., preferably between 100.degree. C.
and 150.degree. C., including all ranges and subranges
therebetween.
[0038] In the case of a copolymer wax, it is preferable to have,
based on the total weight of the copolymer backbone, 0.1 to 30% by
weight of structural units originating from the one monomer and
70.0 to 99.9% by weight of structural units originating from the
other monomer. Such homopolymer and copolymer waxes can be made,
for example, by the process described in EP 571 882, the entire
contents of which is hereby incorporated by reference, using the
metallocene catalysts specified therein. Suitable preparation
processes include, for example, suspension polymerization, solution
polymerization and gas-phase polymerization of olefins in the
presence of metallocene catalysts, with polymerization in the
monomers also being possible.
[0039] Polar modified waxes can be produced in a known manner from
the hompopolymers and copolymers described above by oxidation with
oxygen-containing gases, for example air, or by graft reaction with
polar monomers, for example maleic acid or acrylic acid or
derivatives of these acids. The polar modification of metallocene
polyolefin waxes by oxidation with air is described, for example,
in EP 0 890 583 A1, and the modification by grafting is described,
for example, in U.S. Pat. No. 5,998,547, the entire contents of
both of which are hereby incorporated by reference in their
entirety.
[0040] Acceptable polar modified waxes include, but are not limited
to, homopolymers and/or copolymers of ethylene and/or propylene
groups which have been modified with hydrophilic units such as, for
example, maleic anhydride, acrylate, methacrylate,
polyvinylpyrrolidone (PVP), etc. Preferably, the C2-C3 wax has from
about 0.5% to about 10% hydrophilic units, more preferably from
about 1% to about 8% hydrophilic units by weight with respect to
the weight of the wax, including all ranges and subranges
therebetween. Particularly preferred hydrophilically modified waxes
are ethylene and/or propylene homopolymers and copolymers which
have been modified with maleic anhydride units.
[0041] Particularly preferred C2-C3 polar modified waxes for use in
the present invention are polypropylene and/or polyethylene-maleic
anhydride modified waxes ("PEMA," "PPMA." "PEPPMA") commercially
available from Clariant under the trade name LICOCARE or LICOCENE,
Specific examples of such waxes include products marketed by
Clariant under the LicoCare name having designations such as
PP207.
[0042] Other suitable polar modified polymers include, but are not
limited to A-C 573 A (ETHYLENE-MALEIC ANHYDRIDE COPOLYMER; prop
Point, Mettler: 106.degree. C.) from Honeywell, A-C 596 A
(PROPYLENE-MALEIC ANHYDRIDE COPOLYMER; prop Point, Mettler:
143.degree. C.) from Honeywell, A-C 597 (PROPYLENE-MALEIC ANHYDRIDE
COPOLYMER; prop Point, Mettler: 141.degree. C.) from Honeywell,
ZeMac.RTM. copolymers (from VERTELLUS) which are 1:1 copolymers of
ethylene and maleic anhydride, polyisobutylene-maleic anhydride
sold under the trade name ISOBAM (from Kuraray),
polyisoprene-graft-maleic anhydride sold by Sigma Aldrich,
poly(maleic anhydride-octadecene) sold by Chevron Philips Chemical
Co., poly (ethylene-co-butyl acrylate-co-maleic anhydride) sold
under the trade name of Lotader (e.g. 2210, 3210, 4210, and 3410
grades) by Arkema, copolymers in which the butyl acrylate is
replaced by other alkyl acrylates (including methyl acrylate
[grades 3430, 4404, and 4503] and ethyl acrylate [grades 6200,
8200, 3300, TX 8030, 7500, 5500, 4700, and 4720) also sold by
Arkema under the Lotader name, and isobutylene maleic anhydride
copolymer sold under the name ACO-5013 by ISP.
[0043] According to other embodiments of the present invention, the
polar modified polymer is not a wax. In accordance with these
embodiments of the present invention, the polar modified polymer is
based upon a homopolymer and/or copolymer of hydrophobic monomer(s)
and has a weight-average molecular weight Mw of less than or equal
to 1,000,000 g/mol, preferably of 1000 to 250,000 g/mol and
particularly preferably of 5,000 to 50,000 g/mol, including all
ranges and subranges therebetween.
[0044] In accordance with these embodiments, the polar modified
polymer can be of any form typically associated with polymers such
as, for example, block copolymer, a grafted copolymer or an
alternating copolymer. For example, the polar modified polymer can
contain a hydrophobic backbone (such as polypropylene and/or
polyethylene) onto which hydrophilic groups (such as maleic
anhydride) have been attached by any means including, for example,
grafting. The attached groups can have any orientation (for
example, atactic, isotactic or syndiotactic along the
backbone).
[0045] Preferably, the polar modified polymer(s) represent from
about 1% to about 30% of the total weight of the composition, more
preferably from about 3% to about 20% of the total weight of the
composition, and most preferably from about 5% to about 15%,
including all ranges and subranges therebetween.
[0046] Reaction Product
[0047] According to preferred embodiments of the present invention,
the oil-soluble polar modified polymer is reacted with the
polyamine compound, in the presence of water in, at minimum, an
amount sufficient to solubilize the polyamine, to form a reaction
product. In accordance with the preferred embodiments, the reaction
product is water-insoluble.
[0048] Although not wanting to be bound by any particular theory,
it is believed that at a temperature below 100.degree. C., the
reaction of the oil-soluble polar modified polymer with the primary
amine group of the polyamine opens the anhydride ring to form a
half acid and half amide crosslinked product. However, at a
temperature above 100.degree. C., the reaction of the oil-soluble
polar modified polymer with the primary amine group of the
polyamine opens the anhydride ring to form an imide crosslinked
product. The former product is preferred over the latter product.
It is not necessary for all amine groups and all hydrophilic groups
to react with each other to form the reaction product. Rather, it
is possible that the composition may contain free polyamine and/or
free oil-soluble polar modified polymer in addition to the reaction
product.
[0049] Although not wanting to be bound by any particular theory,
it is also believed that the polyamine(s) can be non-covalently
assembled with the polar modified polymer(s) by electrostatic
interaction between an amine group of the polyamine and a
hydrophilic group (for example, carboxylic acid group associated
with maleic anhydride groups) of the polar modified polymer to form
a supramolecule. For example, with specific reference to maleic
anhydride groups, in the presence of water these groups can open to
form dicarboxylic acid groups which can interact with protonated
primary amines of the polyamine through ionic interaction to form a
polymer-polymer complex with hydrophilic core crosslinkers and a
hydrophobic network that act as supramolecular capsule. If a large
amount of maleic anhydride groups are present, the secondary amine
groups of polyamine are also protonated and interact with alkyl
carboxylates.
[0050] According to preferred embodiments, the oil-soluble polar
modified polymer is in an oil carrier, and the polyamine compound
is in an aqueous carrier, and the reaction occurs by combining the
oil carrier and the aqueous carrier. Because the oil-soluble polar
modified polymer is typically solid at room temperature, the oil
carrier is preferably heated to liquefy the polymer prior to
combination with the aqueous carrier. Preferably, the oil carrier
is heated beyond the melting point of the oil-soluble polar
modified polymer, typically up to about 80.degree. C., 90.degree.
C. or 100.degree. C.
[0051] Without intending to be bound by any particular theory, it
is believed that the reason for this is that due to the chemical
and physical reactions which take place when the oil-soluble polar
modified polymer is combined with the polyamine, the subsequent
reaction product that is formed is surprisingly and unexpectedly
able to entrap large amounts of water molecules within its
hydrophobic matrix. The resultant product is eminently capable of
forming a film, is self-emulsifying, waterproof. Moreover, the
product is both stable and capable of carrying various types of
ingredients.
[0052] Non-Volatile Oil for the Oil-Soluble Polar Modified
Polymer
[0053] The cosmetic compositions of the present invention comprise
at least one non-volatile oil capable of solubilizing the
oil-soluble polar modified polymer. As used herein, the term
"non-volatile" means having a boiling point of greater than about
100.degree. C.
[0054] Examples of non-volatile hydrocarbon oils which may be used
include, but are not limited to, non-polar oils such as branched
and unbranched hydrocarbons and hydrocarbon waxes including
polyolefins, in particular Vaseline (petrolatum), paraffin oil,
squalane, squalene, hydrogenated polyisobutene, hydrogenated
polydecene, polybutene, mineral oil, pentahydrosqualene, and
mixtures thereof.
[0055] Examples of non-volatile oils that may be used in the
present invention include, but are not limited to, polar oils such
as: [0056] hydrocarbon-based plant oils with a high triglyceride
content consisting of fatty acid esters of glycerol, the fatty
acids of which may have varied chain lengths, these chains possibly
being linear or branched, and saturated or unsaturated; these oils
are especially wheat germ oil, corn oil, sunflower oil, karite
butter, castor oil, sweet almond oil, macadamia oil, apricot oil,
soybean oil, rapeseed oil, cottonseed oil, alfalfa oil, poppy oil,
pumpkin oil, sesame seed oil, marrow oil, avocado oil, hazelnut
oil, grape seed oil, blackcurrant seed oil, evening primrose oil,
millet oil, barley oil, quinoa oil, olive oil, rye oil, safflower
oil, candlenut oil, passion flower oil or musk rose oil; or
caprylic/capric acid triglycerides, for instance those sold by the
company Stearineries Dubois or those sold under the names Miglyol
810, 812 and 818 by the company Dynamit Nobel; [0057] synthetic
oils or esters of formula R.sub.5COOR.sub.6 in which R.sub.5
represents a linear or branched higher fatty acid residue
containing from 1 to 40 carbon atoms, including from 7 to 19 carbon
atoms, and R.sub.6 represents a branched hydrocarbon-based chain
containing from 1 to 40 carbon atoms, including from 3 to 20 carbon
atoms, with R.sub.6+R.sub.7 10, such as, for example, Purcellin oil
(cetostearyl octanoate), isononyl isononanoate, C.sub.12 to
C.sub.15 alkyl benzoate, isopropyl myristate, 2-ethylhexyl
palmitate, and octanoates, decanoates or ricinoleates of alcohols
or of polyalcohols; hydroxylated esters, for instance isostearyl
lactate or diisostearyl malate; and pentaerythritol esters; [0058]
synthetic ethers containing from 10 to 40 carbon atoms; [0059]
C.sub.8 to C.sub.26 fatty alcohols, for instance oleyl alcohol; and
[0060] mixtures thereof.
[0061] The at least one non-volatile oil is preferably present in
the composition of the present invention in an amount of from about
0.5% to about 15% by weight, such as from about 1% to about 10% by
weight, such as from about 2% to about 5% by weight, including all
ranges and subranges therebetween, all weights being based on the
total weight of the composition.
[0062] Water
[0063] The composition of the present invention also contains
water. The water is typically present in an amount of from about 5%
to about 50% by weight, such as from about 10% to about 40% by
weight, such as from about 25% to about 35% by weight, including
all ranges and subranges therebetween, all weights being based on
the total weight of the composition. According to particularly
preferred embodiments, sufficient water is present to form a
water-in-oil emulsion.
[0064] Volatile Solvent
[0065] The compositions of the present invention include at least
one volatile solvent. The volatile solvent is preferably chosen
from a volatile silicone oil or a volatile non-silicone oil.
[0066] Suitable volatile silicone oils include, but are not limited
to, linear or cyclic silicone oils having a viscosity at room
temperature less than or equal to 6 cSt and having from to 7
silicon atoms, these silicones being optionally substituted with
alkyl or alkoxy groups of 1 to 10 carbon atoms. Specific oils that
may be used in the invention include octamethyltetrasiloxane,
decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,
heptamethyloctyltrisiloxane, hexamethyldisiloxane,
decamethyltetrasiloxane, dodecamethylpentasiloxane and their
mixtures. Other volatile oils which may be used include KF 96A of 6
cSt viscosity, a commercial product from Shin Etsu having a flash
point of 94.degree. C. Preferably, the volatile silicone oils have
a flash point of at least 40.degree. C.
[0067] Non-limiting examples of volatile silicone oils are listed
in Table 1 below.
TABLE-US-00001 TABLE 1 Viscosity Compound Flash Point (.degree. C.)
(cSt) Octyltrimethicone 93 1.2 Hexyltrimethicone 79 1.2
Decamethylcyclopentasiloxane 72 4.2 (cyclopentasiloxane or D5)
Octamethylcyclotetrasiloxane 55 2.5 (cyclotetradimethylsiloxane or
D4) Dodecamethylcyclohexasiloxane 93 7 (D6)
Decamethyltetrasiloxane(L4) 63 1.7 KF-96 A from Shin Etsu 94 6 PDMS
(polydimethylsiloxane) DC 56 1.5 200 (1.5 cSt) from Dow Corning
PDMS DC 200 (2 cSt) from Dow 87 2 Corning PDMS DC 200 (3 St) from
Dow 102 3 Corning
[0068] Suitable volatile non-silicone oils may be selected from
volatile hydrocarbon oils, alcohols, volatile esters and volatile
ethers. Examples of such volatile non-silicone oils include, but
are not limited to, volatile hydrocarbon oils having from 8 to 16
carbon atoms and their mixtures and in particular branched C.sub.8
to C.sub.16 alkanes such as C.sub.8 to C.sub.16 isoalkanes (also
known as isoparaffins), isododecane, isodecane, and for example,
the oils sold under the trade names of Isopar or Permethyl, the
C.sub.8 to C.sub.16 branched esters such as isohexyl or isodecyl
neopentanoate and their mixtures. Preferably, the volatile
non-silicone oils have a flash point of at least 40.degree. C.
[0069] Non-limiting examples of volatile non-silicone oils are
listed in Table 2 below.
TABLE-US-00002 TABLE 2 Compound Flash Point (.degree. C.)
Isododecane 43 Propylene glycol n-butyl ether 60 Ethyl
3-ethoxypropionate 58 Propylene glycol methylether acetate 46
Isopar L (isoparaffin C11-C13) 62 Isopar H (isoparaffin C11-C12)
56
[0070] In general, the at least one volatile solvent is present in
the composition in an amount of from about 5 to about 80% by
weight, such as from about 10% to about 60% by weight, and from
about 20% to about 40% by weight, including all ranges and
subranges therebetween, all weights being based on the total weight
of the composition.
[0071] Optional Ingredients
[0072] The composition of the present invention may also include
any one, or more, optional ingredients. Examples thereof include,
but are not limited to, colorants such as pigments and dyestuffs,
co-solvents, waxes (if wax is present, preferably it is present in
an amount of less than 1% by weight of the composition, less than
0.5% of the composition, less than 0.25% of the composition,
including all ranges and subranges therebetween), plasticizers,
preservatives, fillers, active ingredients, film formers and
sunscreens.
[0073] It has surprisingly been discovered that the composition of
the present invention forms a stable, waterproof, washable
emulsion, having a unique texture and feel, without the need for
having to employ a surfactant/emulsifier to form the emulsion.
Without intending to be bound by theory, it is believed that the
combination of the polyeamine and oil-soluble polar modified
polymer forms a matrix capable of entrapping ingredients and/or
phases of the composition. Consequently, when a user washes the
composition from the eyes, the water entrapped within the matrix is
released, thereby allowing the composition to be easily removed
from the eyelashes and/or eyebrows.
[0074] Moreover, the composition is washable with water without the
need for having to employ conventional latex film forming
polymers.
[0075] The composition of the present invention possesses a unique
texture and feel, analogous to a bouncy/cushiony gel, which is
characterized by its rheological parameters such as low storage
modulus and high yield strain.
[0076] Rheology
[0077] The rheological properties of the mascara composition, in
accordance with the present invention, are determined by using a
controlled stress rheometer, commercially available from TA
Instruments under the name AR-G2. The samples are measured using a
parallel plate having a stainless steel, cross hatched, 40 mm
diameter plate. The gap is set at 1,000 microns. The desired
temperature is precisely controlled by a Peltier system.
[0078] The mascara sample is transferred to the rheometer, and held
at 25.degree. C. for reaching temperature equilibrium. For a
dynamic oscillation measurement, the sample is pre-sheared at a
shear rate of 100 (1/second) for 30 seconds, and followed by one
minute to reach equilibrium condition. The linear viscoelastic
region is determined by the oscillation strain sweep mode from
10.sup.-3% to 2.times.10.sup.3% of strain, at a constant frequency
.omega. of 1 rad/s. The region at which the elastic modulus or
storage modulus G' is independent of % oscillation strain with an
increasing oscillation strain is defined as the linear viscoelastic
region. The yield strain value is determined from the region at
which the elastic modulus or storage modulus G' begins to be
dependent on oscillation strain. After reaching this critical yield
strain, the internal material structure is disrupted and the
mascara composition is no longer a part of the linear viscoelastic
region.
[0079] A low storage modulus G' at frequency .omega. of 1 rad/s
provides improved wetting property and less creep resistance for
the mascara composition upon application to the eye lashes. The
present invention has a storage modulus G' ranging from about 10 Pa
to about 5000 Pa.
[0080] It has been surprisingly and unexpectedly discovered that
the gel-form composition of the present invention possesses a low
storage modulus G' but at the same time a high yield strain ranging
from about 1% to about 500%. A high yield strain enables the
composition to maintain its structure, thus its stability, under
high stress or strain conditions.
[0081] The shear viscosity .eta.({dot over (.gamma.)}) of the
mascara composition is measured in the flow mode. Before measuring
the shear viscosity, the sample is pre-sheared at a shear rate {dot
over (.gamma.)} of 100 (1/second) for 30 seconds, and allowed to
rest for one minute to reach equilibrium condition. Then, viscosity
of the sample is measured in the continuous ramp mode from
10.sup.-3 (1/second) to 10.sup.2 (1/second) for 10 minutes. The
degree of shear thinning is determined from the slope of log-log
curve of .eta.({dot over (.gamma.)}) versus shear rate {dot over
(.gamma.)}.
[0082] A high value of the shear viscosity .eta.({dot over
(.gamma.)}) at low shear rate provides for longer wear of the
composition and high stability of structure at rest. A high degree
of shear thinning of the composition is desirable in order to
achieve easy and effective application of the mascara composition
onto eye lashes. It has been both surprisingly and unexpectedly
found that the composition of the present invention, in gel form,
possesses the desired high degree of shear thinning, ranging from
about -0.65 to about -0.99.
[0083] The present invention is further described in terms of the
following non-limiting examples. Unless otherwise indicated, all
parts and percentages are on a weight-by-weight percentage
basis.
Example 1-2
Washable Mascara
TABLE-US-00003 [0084] Phase Component Example 1 Example 2 A
Caprylic/capric 1.0 1.0 Triglyceride A Propylene-ethylene- 7.0 7.0
Maleic Anhydride Copolymer A Isohexadecane 2.33 2.33 A Iron Oxides
8.0 8.0 A Isododecane 39.92 40.42 A Propylparaben 0.2 0.2 B DI
Water 34 34.5 B Disodium EDTA 0.1 0.1 B Potassium Cetyl Phosphate 2
2 B Methylparaben 0.25 0.25 B Pentylene Glycol 2 2 B
Polyethyleneimine (PEI- 2 1 35) C Simethicone 0.1 0.1 D
Phenoxyethanol(and) 1.1 1.1 Methylparaben(and)
Isopropylparaben(and) Isobutylparaben(and) Butylparaben Total 100
100
Procedures
[0085] 1. In the main beaker A, the following were added
Isododecane, Caprylic/capric Triglyceride,
Polypropylene-ethylene-Maleic Anhydride Copolymer wax,
Propylparaben. The contents were then heated to 90.degree. C. until
all solids melted. 2. Added Iron Oxides into main beaker and
started homogenizing batch for 1 h at 850 RPM. (Temperature
maintained at 85-90.degree. C.) 3. In another beaker B, added
deionized water, Disodium EDTA, Potassium Cetyl Phosphate,
Methylparaben, Pentylene Glycol. Mixed until uniform. Heated
contents to 90.degree. C. 4. In beaker B, added PEI; then mixed
until PEI dissolved. (Temperature maintained at 85-90.degree. C.)
5. Slowly added contents of beaker B to beaker A. Then added
Simethicone to the mixture. The gel formation was observed in 5
minutes after mixing A and B. 6. During the gel formation, slowed
down the mixing speed from 250 RPM to 100 RPM to 50 RPM. 7. Once
the gel network became thick enough, changed to sweep blade.
Started cooling using 50 RPM. 8. At 35.degree. C., added a mixture
of Phenoxyethanol (and) Methylparaben (and) Isopropylparaben (and)
Isobutylparaben (and) Butylparaben. 9. Continued cooling to
25.degree. C.
Rheological Properties of Examples 1-2
TABLE-US-00004 [0086] Physical G' in Critical Viscosity State of
linear Yield at Degree the region Strain 0.05 1/s of Shear Example
composition (Pa) (%) (Pa s) Thinning 1 Soft Gel 422.8 113 3514
-0.99 2 Softer Gel 60.1 160 379 -0.68
* * * * *